CN103007963B - Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier - Google Patents
Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier Download PDFInfo
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Abstract
The invention discloses a method for preparing a bimetallic nanometer alloy composite material by taking graphene as a carrier. The method comprises the following steps of: by taking a precious metal N salt (N=Pd, Pt) and a transition metal M salt (M=Co, Ni and Cu) as precursors and taking graphene oxide as a matrix, reducing the components by employing a reducing agent; and finally, washing, filtering, drying, grinding and roasting to obtain the high-purity graphene bimetallic nanometer composite material. The composite material has high nanoparticle load capacity, stable structure, high uniformity and high dispersing property, has high binding force with the graphene and is high-efficiency in preparation method, low in cost, simple in process and suitable for industrial production. The composite material can be widely applied to the fields of magnetic targeting materials, various catalysts, electromagnetic shielding wave-absorbing materials, super-capacitor electrode materials and other related function materials.
Description
One, technical field
The present invention relates to a kind of preparation method of take the composite that Graphene is carrier, specifically a kind of preparation method of take the bimetal nano alloy composite materials that Graphene is carrier, belongs to nano inorganic material technical field.
Two, background technology
Nano material size is at nanoscale (1～100nm), between microcosmic and macroscopic view, there are quantum size effect, small-size effect, surface and interface effect, macro quanta tunnel effect etc. and be different from general properties of materials, for example fusing point, magnetic, optics, heat conduction, conductive characteristic etc., often be different from the character that this material shows when integrality, be widely used in each industrial circles such as metallurgy, coating, material manufacture, fine chemistry industry.In recent years, increasing researcher starts precious metals pt, Pd nano material to participate in chemical reaction system as catalyst, improves original harsh reaction condition, makes reaction system become gentle, and can improve reaction efficiency.In industrialization technology application, the expensive and scarcity of resources due to precious metals pt, Pd, is subject to the restriction of the many factors such as cost, recovery technology, does not meet the requirement of Green Chemistry.Much research shows, with noble metal N (N=Pt, Pd) and transition metal M (M=Co, Cu, Ni) alloy material that interacts and prepare, by the cooperative effect between alloy constituent element, electronic effect, makes alloy material show stronger chemistry and physical property.
For the preparation of binary nano-alloy crystal, mainly contain mechanical alloying method, reducing process, supercritical ultrasonics technology (claiming again chemical method), pulse electrodeposition method, metal reaction method and liquid phase dispersion method etc.In the method for above-mentioned preparation, mechanical alloy method efficiency is not high, and gained grain diameter is larger, and skewness, and the Nanoalloy of preparing is generally confined to spherical or class is spherical; Supercritical ultrasonics technology is the alloying pellet epigranular of preparing, and better dispersed, but particle is slightly large.Compare above several method, reducing process is a kind of simple and effective method of preparing Nanoalloy particle.This method be take redox reaction as basis, first in solvent, utilizes suitable reducing agent that metal ion is restored two kinds of metal salt solutions or metallo-organic compound, then acts on mutually with dressing agent and prepares the alloying pellet that dressing agent is modified.Particle composition can belong to by controlling GOLD FROM PLATING SOLUTION the concentration, temperature, reducing agent of ion etc. to be controlled, and the Nanoalloy particle of preparation is less, uniform ingredients, and there is stronger non-oxidizability.But Nanoalloy particle, because its larger specific area is very easily reunited in preparation process, causes activity decreased.Therefore need to find suitable carrier to make loaded nano double metallic composite material, improve its physical and chemical performance, be beneficial to recycling use, reduce costs.
The structure of carrier and its physicochemical properties, as electric conductivity, specific area etc. can significantly affect the interaction between carrier and metal, thereby affect the catalytic performance of catalyst.Traditional carrier comprises material with carbon element, Al
2o
3, molecular sieve etc., and material with carbon element (graphite, CNT, the active carbon) support materials common with other compared, and has been subject to paying close attention to widely in a plurality of fields.
Graphene, as one of member of charcoal family, is to pass through sp by carbon atom
2the monolayer honeycomb shape lattice structure that hydridization forms.Graphene is the elementary cell that forms other carbon allotropes, and its excellent physical property has attracted more and more researchers' concern.Specific area such as large, reaches 2630-2965m
2/ g, high mechanical strength and electric conductivity and stability.Than other material with carbon elements, Graphene has more excellent electron transport ability and large specific area, and lower preparation cost, becomes desirable template and carrys out loaded with nano catalyst.Nancy N.Kariuki in 2010 etc. have reported the preparation method (Chem.Mater.2010 that selects charcoal load P d-Cu Nanoalloy composite, 22,4144-4152), after must first preparing Nanoalloy particle in the method, load to again on charcoal, but in preparing alloying pellet process, preparation process is comparatively complicated, the size of wayward particle.Therefore how selecting a kind of method simple, with low cost to prepare the catalyst of graphene-supported alloy nano, is the problem that the present invention solves.
Three, summary of the invention
The present invention aims to provide a kind of preparation method of take the bimetal nano alloy composite materials that Graphene is carrier, and technical problem to be solved is to improve uniformity and the dispersing uniformity of Nanoalloy particle on carrier of Nanoalloy particle size.
The preparation method of the bimetal nano alloy composite materials that Graphene is carrier is take in the present invention, comprises mixing, reduction, separation, washs, is dried, grinds and calcine each unit process:
It is 1g/(100-1000mL that noble metal N salting liquid and transition metal M salting liquid are added to concentration) graphite oxide aqueous solution in and mix, with adding reducing agent after lye pH adjustment value >10, in 80-100 ℃ of stirring reaction 3-10 hour, reaction finishes rear centrifugal and washing to neutral, in 60-120 ℃, obtains black powder after being dried and grinding;
Described black powder is placed in to tube furnace, under inert gas shielding, passes into hydrogen reducing calcining 60-120min in 300-400 ℃, and then pass into hydrogen calcining 60-130min in 450-600 ℃ under inertia protection, obtain nanometer N-M/ graphene composite material.The present invention adopts two step calcination methods to process, and the first step adopts low temperature calcination, is in order to remove impurity and to be reduced into alloying pellet; Second step adopts high-temperature calcination, and object is to improve the crystalline structure of composite.
Described noble metal N salt is the solubility divalent salts of precious metals pd or Pt;
Described transition metal M salt is the solubility divalent salts of transition metal Co, Ni or Cu;
In described noble metal N salt and described transition metal M salt, the mol ratio of precious metal element and transition metal is 0.1-10:1, and the quality sum of precious metal element and transition metal and the mass ratio of graphene oxide are 1:2-400;
Described reducing agent is selected from sodium borohydride or hydrazine hydrate, and the mass ratio of described sodium borohydride and described graphene oxide is 1:5-10, and described hydrazine hydrate is 20-100mL:1g with the volume mass ratio of described graphene oxide.
Described alkali lye is selected from NaOH solution, KOH solution or ammoniacal liquor.
Described inert gas is selected from nitrogen or argon gas, and the volume ratio of inert gas and hydrogen is 1-10:1.
The flow-control of inert gas is at 0.1-1.0L/min.
The load factor of nanometer N-M/ graphene composite material of the present invention is 0.5-50%, and the quality of nanometer N-M particulate load accounts for the percentage of composite gross mass.
The present invention be take the bimetal nano alloy composite materials that Graphene is carrier and can be noted the graphene composite material as nanometer N-M/ by abridging, and its projection Electronic Speculum (TEM) is presented at Graphene surface and has deposited more equably nanometer N-M particle, and its average grain diameter is in 10nm left and right.Its X-ray diffraction curve (XRD) demonstration, the purity of the graphene-supported nanometer N-M particle of preparation is higher, does not have other impurity.
The present invention has the advantages such as process is simple, easy to operate, cost is low, prepared alloyed nanocrystal is uniformly dispersed, impurity content is few.
Four, accompanying drawing explanation
Figure l is nanometer Pd-Co/ graphene composite material (Pd:Co=1:1) the TEM photo of embodiment 1 preparation.As can be seen from Figure 1, on Graphene surface, deposited more equably N-M particle, its average grain diameter is in 10nm left and right.Particle size range 5-15nm.
Fig. 2 is nanometer Pd-Co/ graphene composite material (Pd:Co=1:1) the EDS photo of embodiment 1 preparation;
Fig. 3 is nanometer Pd-Co/ graphene composite material (Pd:Co=1:1) the XRD figure of embodiment 1 preparation.As can be seen from Figure 3, bimetal nano alloy of the present invention has higher purity.
Five, the specific embodiment
Content of the present invention is further elaborated by following embodiment and accompanying drawing, but does not limit the scope of the invention.
Embodiment 1:
Take 0.282mmol PdCl
2and 0.282mmol Co (C (AR)
4h
6o
4) 4H
2o (AR), after mixing, add in the suspension that contains 0.3g graphene oxide, 80-90 ℃ of lower magnetic force stirs 1 hour, then slowly add 50mL ammoniacal liquor (AR) to regulate PH>10, the hydrazine hydrate solution that adds again 35mL mass concentration 85%, under magnetic agitation, react 4 hours, after reaction finishes, centrifugation obtains black solid, extremely neutral with deionized water washing, then at 60 ℃, vacuum drying obtains black chip solid, will after black sheet solid abrasive, obtain uniform black powder;
Black powder is laid on quartz boat, be placed in the flat-temperature zone of tube furnace, under nitrogen atmosphere, (flow is 600mL/min) is warmed up to 300 ℃, passes into hydrogen (flow is 100mL/min), reduction calcining 120 minutes, is cooled to room temperature under nitrogen (flow is 600mL/min) protection; Under nitrogen atmosphere, (flow is 600mL/min) is warming up to 500 ℃ again; pass into hydrogen (flow is 100mL/min) reduction calcining 120 minutes; under nitrogen protection, (flow is 600mL/min) is cooled to room temperature; obtain nanometer Pd-Co/ graphene composite material 123mg; in composite, Pd and Co mol ratio are 1:1, and the load factor of nanometer Pd-Co particle is 37.8%.
Embodiment 2:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is Pd (C
2h
3o
2)
2(AR), obtain nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=1:1) 124mg, the load factor of nanometer Pd-Co particle is 37.5%.
Embodiment 3:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is Pd (NO
3)
2(AR), obtain nanometer Pd-Co/ graphene composite material (mol ratio Pt:Co=1:1) 134mg, the load factor of nanometer Pd-Co particle is 37.5%.
Embodiment 4:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is PtCl
2(AR), obtain nanometer Pt-Co/ graphene composite material (mol ratio Pt:Co=1:1) 137mg, the load factor of nanometer Pt-Co particle is 46.5%.
Embodiment 5:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.423mmol PdCl
2(AR), transition metal M salt is 0.141mmol Co (C
4h
6o
4) 4H
2o (AR), obtains nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=3:1) 112mg, and the load factor of nanometer Pd-Co particle is 47.5%.
Embodiment 6:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.141mmol PdCl
2(AR), transition metal M salt is 0.423mmol Co (C
4h
6o
4) 4H
2o (AR), obtains nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=1:3) 131mg, and the load factor of nanometer Pd-Co particle is 30.4%.
Embodiment 7:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.282mmol PdCl
2(AR), transition metal M salt is 0.282mmol Ni (NO
3)
26H
2o (AR), obtains nanometer Pd-Ni/ graphene composite material (mol ratio Pd:Ni=1:1) 137mg, and the load factor of nanometer Pd-Ni particle is 37.8%.
Embodiment 8:
The preparation method of the present embodiment is with embodiment 1, and different is that noble metal N salt is 0.282mmol PdCl
2(AR), transition metal M salt is 0.282mmol CuSO
4(AR), obtain nanometer Pd-Cu/ graphene composite material (mol ratio Pd:Cu=1:1) 137mg, the load factor of nanometer Pd-Cu particle is 34.9%.
Embodiment 9:
The preparation method of the present embodiment is with embodiment 1, and different is, and reducing agent uses is 50mg sodium borohydride, obtains nanometer Pd-Co/ graphene composite material (mol ratio Pd:Co=1:1), and the load factor of nanometer Pd-Co particle is 37.8%.
Claims (1)
1. a preparation method for the bimetal nano alloy composite materials that the Graphene of take is carrier, is characterized in that operating according to the following steps:
1) noble metal N salting liquid and transition metal M salting liquid being added to concentration is 1g/(100-1000 mL) graphite oxide aqueous solution in and mix, with adding reducing agent after lye pH adjustment value >10, in 80-100 ℃ of stirring reaction 3-10 hour, reaction finishes rear centrifugal and washing to neutral, in 60-120 ℃, obtains black powder after being dried and grinding;
2) described black powder is placed in to tube furnace, under inert gas shielding, in 300-400 ℃, pass into hydrogen reducing calcining 60-120min, and then pass into hydrogen calcining 60-130min in 450-600 ℃ under inertia protection, obtain nanometer N-M/ graphene composite material;
Described noble metal N salt is the solubility divalent salts of precious metals pd or Pt;
Described transition metal M salt is the solubility divalent salts of transition metal Co, Ni or Cu;
In described noble metal N salt and described transition metal M salt, the mol ratio of precious metal element and transition metal is 0.1-10:1, and the quality sum of precious metal element and transition metal and the mass ratio of graphene oxide are 1:2-400;
Described reducing agent is selected from sodium borohydride or hydrazine hydrate, and the mass ratio of described sodium borohydride and described graphene oxide is 1:5-10, and described hydrazine hydrate is 20-100 mL:1 g with the volume mass ratio of described graphene oxide;
Described alkali lye is selected from NaOH solution, KOH solution or ammoniacal liquor;
Described inert gas is selected from nitrogen or argon gas, and the volume ratio of inert gas and hydrogen is 1-10:1; The flow-control of inert gas is at 0.1-1.0 L/min.
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